CN1150810A - Moisture-curable modified acrylic polymer sealant composition - Google Patents
Moisture-curable modified acrylic polymer sealant composition Download PDFInfo
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- CN1150810A CN1150810A CN94194880A CN94194880A CN1150810A CN 1150810 A CN1150810 A CN 1150810A CN 94194880 A CN94194880 A CN 94194880A CN 94194880 A CN94194880 A CN 94194880A CN 1150810 A CN1150810 A CN 1150810A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
A cross-linkable acrylic copolymer having reduced amounts of silane functionalized monomeric units has been found to achieve unexpectedly superior adhesive, cohesive and flexural properties when used in a sealant formulation as compared with known silane functionalized acrylic copolymers. More particularly, it has been found that by reducing the amount of silane functionalized vinyl addition type monomer to less than 1 molar part per 100 molar parts of (meth)acrylate monomer, and reducing the amount of mercaptosilane chain transfer agent to less than 1 molar part per 100 molar parts of (meth)acrylate monomer, it is possible to obtain a copolymer which is capable of being used in a sealant formulation which exhibits vastly improved elastic properties, which are important for high movement sealant formulations, and improved adhesion to metal and glass substrates, while retaining other important sealant properties.
Description
The present invention relates to be suitable for preparing single-component, that have package stability but be exposed under about room temperature can the wet modified acrylic acid terpolymer that causes the curing sealant composition of rapid solidified under the ambient moisture.The curing sealant that forms has good intensity, elastic recovery rate and weathering resistance, and various grounds are had binding property.The invention still further relates to the method for making this class modified acrylic acid terpolymer, relate to and utilize that modified acrylic acid terpolymer manufacturing of the present invention is at room temperature wettable to be caused the solidified encapsulant composition and exposed certain hour and solidified the solidified encapsulant composition that obtains under envrionment conditions by encapsulant composition of the present invention.
Be mixed with can with radical polymerization and on Siliciumatom bonding the monomeric curable polyacrylate polymkeric substance of organosilane of hydrolysable group is arranged is well-known, to as polymeric viscosifiers and undercoat coating.But after solidifying, these known polyacrylic ester-organosilane compositions generally are flexible, often are hard brittle materials, and this material should not be used for the purposes of the joint seal aspect of elasticity of demand performance.The example of this based composition is open in U.S.PatentNo.3453136,3951893,4026826 and 4093673.
Plueddemann in U.S.Patent No3453230, disclose relate to have " sealing agent of potential industrial utility value, coating and molding compounds ... " acrylate-silicon composition.More particularly, a kind of 100 molar part vinyl ester or acrylic ester unit that mainly contain are disclosed; 1-8 molar part (methyl) propenyloxy group alkyl silane or vinyl silanes; 50 molar part are selected from the optional vinyl monomer of ethene, vinylchlorid, vinylidene chloride, vinyl acetate, vinylbenzene, vinyl cyanide and divinyl at the most; And the multipolymer of the hydrosulphonyl silane of 0.5-4 molar part or amine-thiol chain transfer agents.By the sealing agent that utilizes acrylate-Organosiliconcopolymere preparation of Plueddemann patent disclosure, because bad force of cohesion should not be used for highly ambulant sealant dispensing with the elongation performance.
Known acrylate-Organosiliconcopolymere should not be used for the prescription of high mobility sealing agent, as in the sealing with the structure seam between the material of construction of different heat expansion coefficient.Therefore the existing simultaneously various suitable surrogates such as the prescription of Resins, epoxy or polyurethane-base have reduced the interest of high-performance acrylic acid ester-Organosiliconcopolymere base high mobility sealant dispensing and have slowed down the speed of exploitation.Therefore, though had realized that the potential industrial applicibility of this multipolymer in sealant dispensing as far back as 1964, but, contain the also unexposed mistake of acrylic copolymer reactive silyl-group, that can be used for high hydrodynamic reciprocating sealing agent prescription and that after curing, have good elongation, elastic recovery rate and weathering resistance.
Except that have good physicals such as high elongation rate, tensile strength after solidifying, bondingly peel off, weathering resistance and the flexibility, sealant dispensing should have certain performance before curing, as good long term stability or storage period, good processing property are arranged under normal condition, as high rate of extrusion, fast setting and reach final curing performance rapidly and when on bottom material, applying, good sag prevention performance is arranged before completely solidified with vertical direction.
The patent disclosure of Plueddemann can in encloses container, keep than stable composition.But, have found that, place encloses container to contain that viscosity index has increased by one times under the suitable stablizer condition in 90 days not having by the encapsulant composition of the disclosed vinylformic acid of Plueddemann-organosilane multipolymer, this means that within a short period of time, processing property was lost substantially.
Move the common stopping composition of using the sealant compositions of pbz polymer weight polymers or multipolymer as seam in building industry in order to satisfy because the ground thermal expansion is desired.In order to satisfy extrudability requirement, the sealant dispensing of pbz polymer weight polymers or multipolymer also must contain relatively large solvent to reduce the viscosity of encapsulant composition.But do not need a large amount of solvents in the sealing agent, because sealing agent a large amount of solvents when solidifying can cause sealing agent significantly to shrink, thereby solvent itself is considered to the potential cause that sealing agent lost efficacy.
Therefore, an object of the present invention is to provide the sealant dispensing of the modified acrylic acid terpolymer that is mixed with the monomeric unit that contains hydrolyzable silyl-group, wherein the molecular-weight average of multipolymer to satisfy when solvent load is low, have qualified extrudability, thereby can eliminate basically or can significantly reduce at least in cure period because the seal failure that contraction causes.
Main purpose of the present invention provides and contains the modified acrylic acid terpolymer with hydrolyzable silyl-group monomeric unit, and the wettable solidified that causes that modified acrylic acid terpolymer is suitable for preparing single component has good and isostatic stability, operability and solidify before the sag prevention performance; Have good final curing performance such as good elongation, suitable tensile strength, various grounds are had good binding property, also have good weathering resistance and kindliness; And can solidify rapidly, so that be exposed to the encapsulant composition that can reach final curing performance under the ambient moisture rapidly in room temperature.
Another object of the present invention provides the linking agent/stabiliser system of the sealant dispensing that is used for containing modified acrylic acid terpolymer of the present invention, to prevent because of mistake less water being introduced the forfeiture that early hydration, gelling and processing property take place in the sealing agent at lay up period.
Have been found that, in copolymer skeleton, be mixed with the monomeric modified acrylic acid terpolymer of low levels organosilane, when being used for according to sealant dispensing of the present invention, unexpectedly improve elongation, modulus and to the bounding force of various material of construction grounds (as glass, aluminium), and kept final tensile strength.More specifically say, have been found that, in order to reach noticeable raising is being arranged aspect elongation, modulus and the bounding force, and keep other required performance usually, must adopt than what Plueddemann proposed in U.S.Patent No.3453230 to contain (methyl) acryloxyalkyl silane monomer, vinyl silane monomer and the lower acrylic copolymer of hydrosulphonyl silane chain-transfer agent unit total amount.Specifically, acrylic copolymer of the present invention contains and is lower than 1% (mole) organosilane monomeric unit, and the acrylic copolymer of prior art contains 1% to up to 11% (mole) organosilane monomeric unit.By inference, when organosilane monomeric unit content is low in each acrylic copolymer molecule, can cause lower cross-linking density, thereby obtain a kind of soft, submissiveer encapsulant composition, simultaneously can keep other desirable performance unexpectedly, as final tensile strength with the stress rupture assay determination.
According to another form of the present invention, comprise that in sealant dispensing organic silane monomer unit content is than the low acrylic copolymer of prior art and contain two and trifunctional organosilane linking agent, this linking agent is also as moisture scavenger, to improve package stability and to give the over-all properties of good sealing agent performance.The mixture of two senses and trifunctional silane crosslinker is considered to produce be lower than and adopts the cross-linking density of other linking agent as having only trifunctional or four functional crosslinkers to be produced, therefore excessively crosslinked in the time of can preventing to solidify, thus make curing sealant composition reach the comprehensive state of beyond thought good cohesive strength, bond strength, kindliness and all performances of high mobility.
According to another form of the present invention, have now found that, when the low molecular weight aliphatic monohydroxy-alcohol during as solvent/additive, can improve the sealing agent performance with acrylic copolymer of the present invention and organosilane linking agent.Specifically, have been found that to add fashionablely as solvent or solubility promoter additive when alcohol, unexpectedly improved the raising of elastic recovery rate and other important sealing agent performance is not produced injurious effects.
Acrylic copolymer of the present invention.Organosilane linking agent and unary alcohol solvent individually or synergistically help to obtain being applicable to the high mobility sealant dispensing of building joint sealing usefulness.The sealing agent prescription has good cohesive strength, bond strength, elongation, elastic recovery rate, package stability, sag prevention and processing property.
The chain polymerization method that acrylic copolymer of the present invention can cause by any suitable free radical comprises that body, solution, suspension or letex polymerization form.But, because containing under water function, acrylic copolymer of the present invention can the moisture of the obvious amount that can cause the early stage hydrolysis of organosilane and then react to each other the formation siloxane bond importantly can not be arranged in converging operation as the organosilane with hydrolysable group of cross-linking set.Most preferably be to form acrylic copolymer with the solution polymerization that free radical causes, wherein the type of solvent and consumption preferably be selected from fact not with monomer reaction and can obviously not influence polymerization, as produce the solvent of remarkable chain transfer effect.Therefore, the consumption of solvent preferably keeps low amount as is lower than 50% (weight) that constitutes reaction soln.For be mixed with on Siliciumatom bonding have hydrolysable group polymerisable monomer the acrylic copolymer free radical polymerization suitable solvents technically be known in the document, comprise benzene,toluene,xylene, chloroform, tetracol phenixin, methyl acetate, ethyl ester ethyl ester, ethylene dichloride, acetone, dioxane, the trimethyl carbinol etc. and aromatic hydrocarbons and aliphatic hydrocrbon.
The comonomer that constitutes acrylic copolymer of the present invention comprises at least a acrylate or methacrylate monomer, at least a acryloxyalkyl silane, methacryloxy alkyl silane or the vinyl silane monomer that contains three hydrolysable group that be bonded to more on Siliciumatom.That choose wantonly but optimal, the monomer that is used for modification and improves physicals (as cohesive strength) is a vinyl polyaddition type comonomer; In case of necessity, but optimal, be to select that bonding has the hydrosulphonyl silane chain-transfer agent of three hydrolysable group at the most on Siliciumatom for use.
General principal monomer or the major portion that constitutes multipolymer at least by a kind of acrylate monomer, methacrylate monomer or their mixture, and main performance by these monomers decision multipolymers.Acrylate that is suitable for and methacrylate monomer comprise the compound by the following formula representative:
R in the formula
1Be hydrogen or methyl group, R
2Be to contain 1 alkyl to about 9 carbon atoms.This compounds example comprises ethyl propenoate, 2-EHA, Jia Jibingxisuanyizhi, butyl acrylate etc.Concrete monomer or the monomer mixture that adopts depends primarily on desired physicals, particularly is decided by desired polymkeric substance kindliness.As everyone knows, just can change the kindliness of polymkeric substance by the size that changes alkyl substituent on the acrylate monomer.Preferred principal monomer for acrylic copolymer of the present invention includes the acrylate of 2-6 atom, and most preferred principal monomer is a butyl acrylate, and this monomer is considered to be used for giving encapsulant composition the most comprehensive required or isostatic performance at present.
Acryloxyalkyl silane, methacryloxy alkyl silane or vinyl silanes addition polymerization monomer can produce cross-linking part along copolymer skeleton under moisture (as ambient moisture) effect.Functionalized silane addition polymerization monomer is expressed from the next usually:
R ' is hydrogen or methyl group in the formula, R
3Be divalent alkyl, y is 0 or 1, R
4Be alkyl, Z is a hydrolysable group, and x is 1,2 or 3.In following formula by R
3The alkylidene group of expression comprises methylene radical, ethylidene, propylidene, 2-methyl propylidene, hexa-methylene etc.Suitable hydrolysising group comprise in the art with document in known those groups, also comprise halogen such as chlorine or bromine, alkoxy grp such as methoxy or ethoxy, acyloxy group such as acetoxyl group or propionyloxy, ketoxime base group such as methyl ethyl ketone oximido group, alkoxyl group alkoxy base etc., what have ketoxime base and alkoxy base is preferred, and methoxyl group and oxyethyl group are most preferred.Functionalized trifunctional silane addition polymerization monomer, i.e. the x monomer that equals 3 wherein is because its cost is lower and be easier to obtain, so be preferred.Suitable functionalized silane addition polymerization monomer comprises methacryloxypropyl trimethoxy silane, acryloxy propyl-triethoxysilicane, vinyltrimethoxy silane etc., and vinyltrimethoxy silane reactive behavior owing to it when the addition polymerization polymerization is lower, can provide non-reactive polymer unitary long-chain containing between the functionalization silane monomer unit of hydrolyzable cross-linking part, therefore be preferred, thereby adopt the functionalized silane monomer of the silyl-group that obtains easily can reach the purpose that reduces cross-linking density with trifunctional side chain.
, therefore, adopt the functionalized silane addition polymerization monomer lower than the disclosed consumption of prior art for thereby the length of the non-reacted part that increases polymer chain makes the more existing better use properties of encapsulant composition to reduce crosslinking degree.Specifically, the monomeric consumption of functionalized silane addition polymerization is lower than 1 (mole) part in the copolymerization of acrylic copolymer of the present invention, preferred about 0.5 to about 0.95 molar part, and most preferably from about 0.5 to about 0.8 molar part (in main (methyl) acrylate monomer of per 100 molar part).
In order to improve performance as improving tensile strength, shearing resistance and cohesive strength, it is preferred utilizing optional vinyl polyaddition type comonomer.The consumption of optional vinyl polyaddition type comonomer is can not have a strong impact on generations such as other performance such as processing property, elasticity, modulus to improve above-mentioned performance to be as the criterion.It is feature that optional vinyl polyaddition type comonomer generally belongs to unsaturated addition polymerization monomer with monoene, do not contain the hydrolysable group that is bonded on the silane atom, generally moisture in the environment is not had reactive behavior, blending can become the integral part of sealant dispensing in acrylic copolymer of the present invention.The vinyl polyaddition type comonomer that the present invention is suitable for comprises aromatic substance such as vinylbenzene, the alpha-methyl styrene etc. of vinyl cyanide, methacrylonitrile, vinyl substituted, and other well-known polyaddition type comonomer that is used to improve physicals.Preferred vinyl addition polymerization monomer comprises vinylbenzene and vinyl cyanide, and vinyl cyanide is most preferred.The consumption of optional vinyl polyaddition type comonomer depends mainly on desired specified property, specific (methyl) acrylate principal monomer and selected specific vinyl polyaddition type comonomer.About at the most 60 (moles) of the monomeric suitable amount ranges of vinyl addition polymerization part, more wish about 10 to about 50 (moles) part, most preferably from about 20 to about 40 (moles) parts (in per 100 parts of (methyl) acrylate principal monomers).
When free radical polymerization acrylic copolymer of the present invention,, preferably adopt chain-transfer agent in order to help to control number-average molecular weight.In order to improve the cohesive strength of solidified sealing agent, preferably adopt the hydrosulphonyl silane chain-transfer agent to be connected on the cross-linking part of copolymer molecule one end.Be applicable to that suitable hydrosulphonyl silane chain-transfer agent of the present invention has following general formula:
HS-R
5-SiR
6 3-xZ
x
R in the formula
5Be divalent alkyl, R
6Be that alkyl, x are 1,2 or 3, Z is a hydrolysable group.Alkylidene group, alkyl group and hydrolysable group normally with described functionalized silane addition polymerization monomer in corresponding group be same or similar.The hydrosulphonyl silane chain-transfer agent that is suitable for comprises gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, thiopurine methyltransferase methyl dimethoxysilane etc., and γ-mercaptopropyl trimethoxysilane is preferred.The consumption of chain-transfer agent is similar with disclosed prior art.
The copolymerization that free radical causes can carry out under temperature and pressure well-known in the art.In order to simplify the operation and to install, copolymerization is preferably at normal pressure or near carrying out under the normal pressure.In order to make the monomer addition polymerization reach maximum irregular distribution, polyreaction is preferably carried out under the top temperature of the risk that does not in fact have depolymerization as far as possible near forming polymkeric substance.Certainly, minimum effective temperature is decided by the dissociation temperature of selected radical initiator.Suitable temperature range is generally about 25 ° to about 200 ℃.Polyreaction is preferably carried out under the reflux temperature of reaction mixture.
Generally, any radical initiator known in the art all can adopt.Suitable radical initiator comprises any acyl peroxide such as acetyl peroxide, benzoyl peroxide, alkyl peroxide such as tert-pentyl and tert-butyl peroxide, hydrogen peroxide such as tertbutyl peroxide and cumyl hydroperoxide; Peresters such as t-butylperoxyl benzoate; Various known azo initiators are as 2,2 '-Diisopropyl azodicarboxylate, and disulphide initiator, the tetrazene etc.The t-amyl peroxy thing is preferred specifically.Initiator amount is identical with the prior art specified amount usually, the suitable consumption of radical initiator can be by those skilled in the art according to specific reaction conditions, and desired end properties (monomer that comprises employing), the molecular weight distribution that requires, used chain-transfer agent (if with) wait definite.The suitable consumption of radical initiator is usually within about 0.01% to 1% scope (in whole total monomer weights).
According to preferred aspect of the present invention, carry out copolymerization with semi-batch mode, promptly infeed the difference that monomer compensates monomer reaction speed to reactor, thereby in polymerization process, keep between monomer concentration ratio constant substantially by predetermined speed.Keeping certain monomer concentration ratio will help to obtain more uniform sequence length in polymerization process distributes.To a specified copolymerization system, those skilled in the art can promptly be added the reactive high monomer of more amount with observing monomer concentration and the suitable easily definite rational monomer feed scheme of monomer feeding rate of adjusting in the periodical operation in polymerization reaction late stage with the monomer of excessive reactivity difference at the polyreaction initial stage.If desired, also can further adjust and improve monomer feed scheme.
For reduction is bonded in the hydrosulphonyl silane chain-transfer agent and is bonded in the danger that early stage hydrolysis takes place owing to the effect that is subjected to accidental small amount of moisture for hydrolysable group on the functionalized silane addition polymerization monomer, and cancellation should keep adiabatic drying to all each components of copolymerization mixture or at least near the requirement that does not have water fully, preferably various linking agents/water-removal agent imported in the copolyreaction mixture.Suitable linking agent/water-removal agent generally comprises the polyfunctional organosilane that contains two to four hydrolysable group.Suitable linking agent/water-removal agent example comprises methyltrimethoxy silane, tetraethyl-or thosilicate, isobutyl-Trimethoxy silane and dimethyl methyl ethyl ketoxime base silane.Four functional organosilanes have good slightly moisture to remove effect, and the trifunctional organosilane is preferred, because it has enough removing moisture effectiveness and makes the solidified encapsulant composition have comprehensive performance (mainly being because lower cross-linking density).During acrylic copolymer copolymerization of the present invention, the preferential linking agent/water-removal agent that adopts is the isobutyl-Trimethoxy silane.Linking agent during copolyreaction/water-removal agent preferred amount ranges is about 0.5 part to about 4 parts, more preferably 1 part to about 2 parts (in every mole of silane to radical polymerization).
This reaction generally can continue to monomer conversion and reach at least 99%, and more preferably monomer conversion about 99% to 99.99%.Reaching the required time of requirement transforming degree is decided by to comprise polymerizing conditions such as temperature, pressure, monomer, key transfer agent, initiator, yet, can reach suitable transformation efficiency in about 3 hours to about 10 hours usually.
The number-average molecular weight that acrylic copolymer of the present invention has usually is about 5000 to about 40000, and more preferably from about 15000 to about 25000, and weight-average molecular weight is 10000 to about 200000, more preferably from about 25000 to about 100000.General each copolymer molecule on average contains about 1 to about 4, most preferably contains about 2 organosilane unit and contains about 2 to about 12, most preferably from about 6 hydrolysable group.
Acrylic copolymer expection of the present invention has the various performances that are applicable to various tackiness agents of manufacturing and formulation for coating material.Have been found that performance with the sealing agent of acrylic copolymer disclosed herein preparation is better than the performance with the similar sealing agent of known acrylic copolymer preparation unexpectedly.
The present invention is wettable to cause blend, linking agent/water-removal agent and the various conventional additives such as filler, tinting material, rheology control agent, extender, solvent, curing catalysts that comprise that the curing sealant composition generally includes acrylic copolymer disclosed herein.
Can adopt known various linking agent/water-removal agents such as methyl methoxy base silane or tetraethyl orthosilicate ester in this area and the document.Yet, according to the preferred form of the present invention, found to adopt the binding substances of two senses and trifunctional linking agent, need not can obtain good unexpectedly package stability by four functional crosslinkers substantially, fast the combination of solidification rate and good curing sealant performance.The mixture that it is believed that two senses and trifunctional silane crosslinker has had the solidified sealing compositions to be used for the required superior elasticity body performance of high hydrodynamic reciprocating sealing agent, and reaches simultaneously or keep the necessary cross-linking density of other good sealing agent performance (as cohesive strength and bond strength, good weathering resistance).The consumption normally about 0.5 of two functional crosslinkers/water stablizer is to about 4 parts, preferred about 1.1 to about 2.0 parts (in 100 parts of weight polymers).Preferred two functional crosslinkers/water-removal agent comprises dialkyl dialkoxy silicane, as dimethyldimethoxysil,ne or vinyl methyl dimethoxysilane.But also can adopt various other two senses and trifunctional silane crosslinker as two senses and trifunctional oximido solidifying agent, as dimethylformamide dimethyl base-ethyl oximino silane.Because dimethylformamide dimethyl base ethyl ketoxime base silane is extremely sensitive to high temperature oxidation, therefore, it is preferred adding this compound after the acrylic copolymer copolymerization.
The consumption of trifunctional linking agent/water-removal agent normally about 0.5 is to about 10 parts, more preferably from about 1.5 to 2.5 parts (in 100 parts of weight polymers).Preferred trifunctional linking agent/water-removal agent is the isobutyl-Trimethoxy silane, it or can after the acrylic copolymer copolymerization, add in the sealant dispensing or more preferably when the acrylic copolymer copolymerization, add, to help to prevent the early stage hydration of hydrolysable group in organosilane addition polymerization monomer and the optional hydrosulphonyl silane chain-transfer agent.In either case, above-mentioned consumption is meant the total amount of two senses and trifunctional linking agent/water-removal agent, need not consider that they are to add or add after the copolymerization when the acrylic copolymer copolymerization.
In order to give sealant dispensing ideal operability, extrudability and sag prevention preferably add rheology control agent in sealant dispensing, the interpolation thixotropic agent of more specifically saying so.Preferred thixotropic agent comprises commercially available castor oil derivative, and its effective level is about 3% to about 8%, and better is about 4% to about 6% (weight is in the sealant dispensing gross weight).
Preferably add any known energy to sealant dispensing and stick to tackifier on the non-porous substrates toughly in order to improve binding property between sealing agent and ground such as glass or the metal.The tackifier that are suitable for contain the multifunctional silane with three hydrolysable group usually, hydroxyl or other oxy radical reaction on these groups and the ground, also can react each other and with acrylic copolymer reaction, the perhaps direct silane by hydrolysis or increase binding property between acrylic copolymer and ground by linking agent.The example of tackifier comprises methacryloxy Trimethoxy silane, γ-Huan Yangbingyangbingjisanjiayangjiguiwan, γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl trimethoxy silicane and aminoalkyl group trimethoxy disilane.The preferred tackifier that are used for sealant dispensing of the present invention are γ-An Jibingjisanyiyangjiguiwan or gamma-amino propyl trimethoxy silicane.The consumption of tackifier is from 0.1 to 0.5 part usually in the sealant dispensing, more preferably from 0.1 to 0.3 part (weight is in 100 parts of weight polymers).
Various mineral fillers and extender can be added in the sealant dispensing to improve its sag prevention.The example comprises as silicon-dioxide, alumina, titanium dioxide, glass powder or glass fibre, carbon black, granulated metal, carclazyte, such class fillers such as talcum, magnesium oxide, magnesium hydroxide, lime carbonate.At present preferred filler is a lime carbonate, thereby because it can hang down saturation state buys from market and avoided to prevent the drying that the acrylic copolymer premature gelation is required, and carclazyte that is purchased and talcum generally must carry out drying to prevent premature gelation.The consumption of filler is decided by other component and desirable performance in the sealant dispensing, but common amount ranges is about 30 to about 100 parts, more preferably from about 65 to about 80 parts (weight is in weight of 100 parts of polymkeric substance).
In order to promote under the moisture effect, to solidify rapidly, it is desirable to add condensation or curing catalysts to sealant dispensing.The condensation catalyst of suitable curing silane-functionalised acrylic copolymer of the present invention is well-known, it comprises the carboxylate salt, organic titanic compound of various alkali metal phenolates, amine, metal and other as the catalyzer among the U.S.Patent No.3453 230 that is disclosed in Plueddemann, and this patent content has been listed the part of this paper as disclosure in.The consumption of condensation catalyst in prescription should be weighed the solidification rate of prescription and the relation of permanent stability.Therefore, it is desirable to use for obtaining the required minimum catalyzer of desirable curing performance.Preferred curing or condensation catalyst are dibutyltin diacetate or dibutyl tin laurate, and its preferred amount ranges is 0.03% to 0.2% (weight) (in the encapsulant composition gross weight).
As needs, can adopt any pigment or tinting material.For example, adopt titanium dioxide to be that tinting material and pearl filler are combined and obtain light-coloured sealant dispensing.
In order to obtain to be fit to the viscosity of operation, total solid content can be by solvent such as benzene in the sealant dispensing, and dilutions such as toluene, dimethylbenzene, chloroform, tetracol phenixin, methyl acetate, ethanol, Virahol are adjusted.The total solid content of sealant dispensing of the present invention is preferably about 98% to about 90% (weight).
According to the particularly preferred form of the present invention, have been found that and add a small amount of lower molecular weight monohydroxy-alcohol in the sealant dispensing that compare with using more conventional solvent (as dimethylbenzene), elastic recovery rate can obtain beyond thought raising.Preferred monoalcohol solvent is a Virahol.
The consumption of solvent is decided by desired encapsulant composition performance and other component, but, observe, compare with the similar prescription that adopts dimethylbenzene, consumption is that the Virahol of 1-10% (weight is in the sealant dispensing gross weight) can significantly improve elastic recovery rate.
Have been found that the encapsulant composition according to mentioned above principle system has advantages of excellent stability and processing property; Near solidifying rapidly under the room temperature, this can and reach final curing performance rapidly by short skinning time, short time of not being clamminess proves; And good curing performance such as good weatherability properties, cohesive strength, bond strength, high reactivity, snappiness, elastic recovery rate etc.
Following embodiment supplies to further specify the present invention so that the present invention is had a better understanding, but should not be considered to limitation of the present invention.
Embodiment
In being housed, the stainless steel reactor of reflux exchanger prepares polymkeric substance.With suitable pump the monomers/initiator fluid-flow pump is gone in the reactor.
The Waters SEC determining molecular weight that DRI and Viscotek detector are equipped with in employing distributes.Carry out monosomic analysis with Hewlett Packard GC and SPB-5 PSI capillary column.
Polymerization is to carry out in the appropriate solvent medium, during beginning partial solvent is sent in the reactor, and remaining solvent is pressed the operational throughput of monomer, initiator and water-removal agent and distributed.Needn't do to remove water treatment to solvent, initiator and monomer especially, and silane monomer/linking agent only needs to handle under the nitrogen atmosphere,
Polymkeric substance under refluxad or under the highest 140 ℃ of temperature prepares.Monomer and initiator were sent in the reactor in 2-3 hour in accordance with regulations.Whole polymerization process takes 4.5 hours.
Adopt Orbital Shaft mixing tank, sealing agent mixes in mixing tank, under nitrogen atmosphere various materials is added in the mixing tank.
Add polymkeric substance and methyl trioxime silane and mixed 3 minutes to clean mixing tank with 900RPM.Add castor oil-base thixotropic agent and titanium dioxide then and mixed 5 minutes, after this, add lime carbonate.Mix and add tackifier and solvent (dimethylbenzene) after 5 minutes, remix adds DBTDA catalyzer and remaining solvent after 5 minutes.
Material in the mixing tank at 20-25 minute internal heating to 65 ℃, and after mixed 10 minutes, is cooled to 50 ℃ with it between 65 ℃ and 68 ℃ of temperature.
Under this temperature, material was carried out vacuum outgas 5 minutes while mixing.Stopping mixing tank then ends to vacuumize and charge in the mixing tank with nitrogen.Under nitrogen gas stream, operate the scraper plate of mixing tank, and material is filled in the suitable tube with hydraulic pressure.
The industrial standards test method comprises:
1) stability is checked the variation (under 60psi push through the 20g material 0.104 inch orifice) of viscosity index at the appointed time.
2) solidification rate is checked in the time of being clamminess (method 2.1; CAN 2-19.0-M77 and ASTM C679), and adopt Zwick measurement of hardness device to check the increase of hardness (Shao Shi " A ") within a certain period of time.
3) flow adopts Boeing Jig Assembly (ASTMD 2202) method.
4) bonding to glass, mortar and aluminium according to method 14.6; CAN2-19.0-M77 carries out bonding stripping test.
5) H-Bead stretches according to method 14.1; CAN2-19.0 M-77 adopts tensile testing machine (Instron trier).
6) locomotivity on glass, bottom mortar and non-bottom mortar adopts circulation method according to method 14.4CAN2-19.0-M77 and ASTMC719.
7) the weather-proof weatherometer of weather-proof aging employing xenon arc
8) elastic recovery rate (ISO 7389).
The wet method summary of solidifying RTV sealing agent polymkeric substance that causes of preparation
Reactor is at first used nitrogen purge, sends into dimethylbenzene then, elevated temperature to 140 ℃, and this moment, the solvent boiling also refluxed.
Silane and main material are pre-mixed in independent container, and each feeding rate metering in accordance with regulations infeeds in the reactor then.In order to control the distribution of reactive different monomers, vinyl silanes and Acrylic Acid Monomer are measured respectively.Polyreaction began in 5-10 minute.When twice feed finished, conversion of monomer was the transformation efficiency of polymkeric substance about 90%.
In order to make residual monomer be brought down below 500ppm (0.05%), step according to the rules infeeds the metering of water-removal agent solution in the reactor.Whole polymerization process is carried out under the reflux temperature of mixture.
Then material in the reactor is cooled to and is lower than 100 ℃, and once add stablizer, mixing, then mixture is drained in the container of anti-steam.
According to principle of the present invention, adopt preferred monomer (butyl acrylate, vinyl cyanide and vinyltrimethoxy silane) and preferred chain-transfer agent (mercaptopropyl trimethoxysilane) preparation acrylic copolymer (being called P1).Also comprise as xylene as solvent, as 3 of radical initiator 3-two (peroxidation tert-pentyl) ethyl butyrate and the isobutyl-Trimethoxy silane (IBTMS) of water-removal agent when the polyreaction in the polymerization reaction mixture.When multipolymer was used for sealant dispensing, IBTMS also can be used as the linking agent after the polyreaction.After finishing, polymerization process adds dimethyl methyl ethyl ketoxime silane immediately.The consumption of the above-listed batching of preparation acrylic copolymer of the present invention is listed in Table I.
Table I
| The P1 weight part | The mole base | The P2 weight part | The mole base | The P3 weight part | Molar weight | |
| Butyl acrylate | ??89.0 | ?100 | ?88.29 | ?100 | ?88.29 | ?100 |
| Vinyl cyanide | ??10.0 | ?27.1 | ?10.00 | ?27.2 | ?10.00 | ?27.2 |
| Vinyltrimethoxy silane | ??0.7 | ?0.68 | ?1.03 | ?1.00 | ?1.03 | ?1.0 |
| Mercaptopropyl trimethoxysilane | ??0.3 | ?0.22 | ?0.68 | ?0.50 | ?0.68 | ?0.50 |
| Dimethylbenzene | ??14.27 | ?-- | ?14.27 | ?-- | ?14.27 | ?-- |
| Initiator | ??0.17 | ?-- | ?0.17 | ?-- | ?0.17 | ?-- |
| Water-removal agent | ??0.75 | ?-- | ?0.75 | ?-- | ?0.75 | ?-- |
In order to contrast, except that the consumption of vinyltrimethoxy silane and mercapto propyl group trimethoxy silane is by the minimum quantity that proposes in the prior art, all the other all adopt monomer same as described above, solvent, initiator and water-removal agent, and prepare similar acrylic copolymer (being called P2) at same equipment with same step.
The acrylic copolymer of second contrast (being called P3), except that not adding any water-removal agent, all the other all are in kind, adopt same component and consumption to prepare.Comparative examples composition P2 and P3 also list in the table 1.
Table II has been listed the performance of preferred copolymer of the present invention and according near the performance of the contrast multipolymer of prior art preparation.
Used multipolymer is respectively the acrylic copolymer of P1, P2 and P3 in the listed sealant dispensing of following table:
| Weight part | |
| Multipolymer | ?49.5 |
| Thixatrol?ST | ?5.4 |
| TiO 2 | ?4.4 |
| Wingdale | ?37.04 |
| Methyl trimethoxy base ethyl ketoxime base silane | ?0.9 |
| The gamma-amino propyl trimethoxy silicane | ?0.2 |
| The dibutyl tin diacetate esters | ?0.06 |
| Dimethylbenzene | ?2.5 |
The above-listed various performances of sealant dispensing (being called S1, S2 and S3) after curing of P1, P2 and P3 of using are respectively listed in the Table III.The result shows, utilizes the prior art multipolymer and do not contain the sealant dispensing (S3) of preferred silane linking agent/water-removal agent of the present invention, increased by one times according to its viscosity index in about 7 days, can illustrate it is more unsettled.The result also shows, adopts multipolymer of the present invention can obtain having the good sag prevention and the sealant dispensing of suitable hardness.The result proves, adopts multipolymer of the present invention can obtain the bond properties of glass and aluminum substrates is better than greatly the sealant dispensing of prior art.Mechanical testing shows that also the sealant dispensing of employing multipolymer of the present invention has good tensile strength (solidified sealing agent) and is equal to mutually with prior art.Presentation of results means that unexpected improvement that exceed that obtains aspect strain and the modulus the desired elastic performance of high hydrodynamic reciprocating sealing agent prescription is greatly improved.
The invention described above multipolymer (P1) is used in two essentially identical sealant dispensings, just adopts Virahol to replace dimethylbenzene in another prescription (S4) in one of them sealant dispensing (S5) as solvent.Adopt each sealant dispensing of multipolymer of the present invention all to demonstrate good operation and sag prevention performance, good bonding stripping performance, the favorable mechanical performance, and each prescription all passed through ASTM C719 nigration (on aluminium, glass and bottom mortar ground ± 25% move), as shown in Table IV.But, wherein adopt Virahol to have excellent elasticity recoverability (ISO 7389, wherein solidify the stretching that sample is subjected to raw footage elongation 100%) as the sealant dispensing of solvent.Contain the Virahol sealant dispensing and reach 72% elastic recovery rate, and cohesive failure takes place in another sealing agent (other composition is identical) that contains xylene solvent before elongation reaches 100%.
Know from above-mentioned explanation and embodiment and to show that with regard to specific embodiment of the present invention, purpose of the present invention reaches.But, be tangible various modification and equivalent to those skilled in the art, should think to belong to the scope and spirit of stipulating in attached claims of the present invention.
Table II
| Polymkeric substance number | Linking agent % | RTI viscosity (handkerchief second) | Polymer solids level % | The gel permeation chromatography data | Explanation | ||||||
| ?IBT ?MS | ??DMO ??S | ???Mn | ?Mw0 ?00’s | ???Mz | ?MW/ ?Mn | ?Skew | |||||
| ?(N) | (W) | ||||||||||
| P1 | ?0.75 | ?1.31 | ?64.3 | ?83.2 | ??16.1 | ?53.1 | ?110.2 | ?3.29 | ?4.4 | 2.56 | Embodiments of the invention |
| P2 | ?0.75 | ?1.31 | ?37.8 | ?83.1 | ??15.3 | ?45.0 | ?86.8 | ?2.94 | ?3.65 | 2.09 | The described functionalized monomer of minimum quantity |
| P3 | ?0 | ?0 | ?46.4 | ?85.1 | ??13.9 | ?51.0 | ?117.6 | ?3.67 | ?5.05 | 2.83 | No water-removal agent or stablizer |
Table III
| Polymkeric substance of the present invention is compared with the standard seal agent prescription with DOW patent scheme | |||||||||
| Sealing agent | Polymkeric substance | Viscosity (second) | Flow (inch) | Shore " A " hardness | Bonding stripping strength on glass (thousand Newton/meter) | The bonding stripping strength of aluminium (thousand Newton/meter) | Tensile stress at break (MPa) | Elongation at break (%) | Modulus (MPa) |
| S1 | P1 | 81 | ?0.03” | 31 | 2.86 | 2.18 | 1.47 | 1.46 | 1.01 |
| S2 | P2 | 31 | ?0.02” | 41 | 1.12 | 1.81 | 1.50 | 98 | 1.53 |
| S3 | P3 | 93 (7 days 190) | ?0.05” | 47 | 1.19 | 1.26 | 1.41 | 91 | 1.55 |
Table IV
| System component | Standard recipe | Improve prescription |
| Polymkeric substance | ?47.50％ | ?47.50％ |
| Trixatrol?ST | ?6.40％ | ?6.40％ |
| TiO2 | ?4.60％ | ?4.60％ |
| Dimethylbenzene | ?2.60％ | |
| Virahol | ?2.60％ | |
| A-1100 (Union Carbide) gamma-amino propyl trimethoxy silicane | ?0.20％ | ?0.20％ |
| OS-1000 (Allied-Signal) methyl trimethoxy base ethyl ketoxime base silane | ?0.90％ | ?0.90％ |
| Wingdale | ?34.73％ | ?34.73％ |
| The dibutyl tin diacetate esters | ?0.07％ | ?0.07％ |
| The dioctyl adipic acid ester | ?3.00％ | ?3.00％ |
| Viscosity index (second) | ?28 | ?25 |
| Boeing Jig flow (inch) | ?0.03 | ?0.02 |
Table IV (continuing)
| Bonding stripping strength (thousand Newton/meter) | ||
| Glass | 2.3C/F | 2.5C/F |
| Aluminium | 1.8C/F | 2.0C/F |
| Mortar | 2.2C/F | 2.0S/F |
| D-Bell maximum stress (MPa) | 0.95 | 0.83 |
| The D-Bell maximum strain | 179％ | 181％ |
| Move: ± 25% ASTM C719 | PASS：G，A，Pm | PASS：G，A，Pm |
| Elastic recovery rate ISO 7389 | C/F | 72％ |
| SHORE " A " hardness | 28 | 21 |
According to patent statute, embodiment preferred and best form have been proposed, scope of the present invention is not limited thereto, and belongs to the scope of attached claim and would rather say so.
Claims (18)
1. acrylic copolymer comprises the copolymerization product that the free radical of following compounds causes:
A) at least a acrylate monomer that is expressed from the next, methacrylate monomer or their mixture:
R ' is hydrogen or methyl group in the formula, R
2Be to contain 2 alkyl to about 8 carbon atoms;
B) contain about 0.05 at least a acrylate monomer of per 100 molar part, methacrylate monomer or their mixture at least a functionalized silane addition polymerization monomer with at least one hydrolysable group of about 0.95 molar part, described functionalized silane addition polymerization monomer is expressed from the next:
R in the formula
1Be hydrogen or methyl group, R
3Be alkylidene group, y is 0 or 1, R
4Be alkyl group, Z is a hydrolysable group, and X is 1,2 or 3;
C) containing about at the most 60 molar part at least a acrylate monomer of per 100 molar part, methacrylate monomer or their mixture does not contain and is bonded in that the monoene of hydrolysable group belongs to unsaturated addition polymerization monomer on the Siliciumatom; And
D) contain at least a acrylate monomer of per 100 molar part, methacrylate monomer or their mixture and be lower than the hydrosulphonyl silane chain-transfer agent that 1 molar part is represented with following formula at the most,
H-S-R
5-SiR
6 3-xZ
x
R in the formula
5Be alkylidene group, R
6Be alkyl group, X is 1,2 or 3, and Z is a hydrolysable group.
2. according to the acrylic copolymer of claim 1, wherein the consumption of component (C) is in per 100 molar part components (a), and for about 20 to about 50 molar part, component (c) is selected from vinyl substituted aromatic, vinyl cyanide and methacrylonitrile.
3. according to the acrylic copolymer of claim 2, wherein the consumption of component (b) is in per 100 molar part components (a), for about 0.05 to about 0.95 molar part, wherein the consumption of component (d) counts about 0.05 to about 0.95 molar part with per 100 molar part components (a).
4. according to the acrylic copolymer of claim 3, wherein component (b) is selected from methoxy group, oxyethyl group group and methyl ethyl ketone oximido group with hydrolysable group (d).
5. according to the acrylic copolymer of claim 4, wherein component (a) is to contain the acrylate of alkyl group of 2 to 9 carbon atoms or their mixture.
6. according to the acrylic copolymer of claim 5.Wherein component (b) is the vinyl alkyl organoalkoxysilane.
7. according to the acrylic copolymer of claim 6, wherein component (a) mainly is a butyl acrylate, and component (b) mainly is that vinyl trialkyl oxysilane, component (c) mainly are that vinyl cyanide and component (d) mainly are sulfydryl alkylidene group trialkoxy silanes.
8. the wettable solidified sealing agent that causes comprises:
A) acrylic copolymer is the copolymerization product of the free radical initiation of following compounds:
A) at least a acrylate monomer that is expressed from the next, methacrylate monomer or their mixture:
R in the formula
1Be hydrogen or methyl group, R
2Be to contain 2 alkyl to about 8 carbon atoms;
B) contain about 0.05 at least a acrylate monomer of per 100 molar part, methacrylate monomer or their mixture at least a functionalized silane addition polymerization monomer with at least one hydrolysable group of about 0.95 molar part, described functionalized silane addition polymerization monomer is expressed from the next:
R in the formula
1Be hydrogen or methyl group, R
3Be alkylidene group, y is 0 or 1, R
4Be alkyl group, Z is a hydrolysable group, and x is 1,2 or 3.
C) containing about at the most 60 molar part at least a acrylate monomer of per 100 molar part, methacrylate monomer or their mixture does not contain and is bonded in that the monoene of hydrolysable group belongs to unsaturated addition polymerization monomer on the Siliciumatom; And
D) contain at least a acrylate monomer of per 100 molar part, methacrylate monomer or their mixture and be lower than the hydrosulphonyl silane chain-transfer agent that 1 molar part is represented with following formula at the most,
H-S-R
5-SiR
6 3-xZ
x
R in the formula
5Be alkylidene group, R
6Be that alkyl group, X are 1,2 or 3, Z is a hydrolysable group.
B) per 100 parts of (weight) acrylic copolymer contain about 0.5 to about 4 parts (weight) two functional silane linking agents, and
C) per 100 parts of (weight) acrylic copolymer contain about 0.5 to about 10 parts of (weight) trifunctional silane crosslinkers.
9. sealing agent according to Claim 8, wherein two functional silane linking agents are dialkyl dialkoxy silicane or dialkyl group two ketoximinosilanes, wherein the trifunctional based cross-linker is alkyl three ketoximinosilanes or alkyl tri-alkoxy silicon kitchen range.
10. according to the sealing agent of claim 9, wherein in the acrylic copolymer consumption of component (C) in per 100 molar part components (a), for about 20 to about 50 molar part, wherein component (C) is selected from vinyl substituted aromatic, vinyl cyanide and methacrylonitrile in the acrylic copolymer.
11. sealing agent according to claim 10, wherein in the acrylic copolymer consumption of component (b) in per 100 molar part components (a), for about 0.5 to about 0.8 molar part, the consumption of component in the acrylic copolymer (d) is in per 100 molar part components (a), be about 0.3 to about 0.7 molar part, wherein component (a) mainly is a butyl acrylate, and component (b) mainly is a vinyl trialkyl oxysilane, component (c) mainly is a vinyl cyanide, and component (d) mainly is a sulfydryl alkylidene group trialkoxy silane.
12. according to the sealing agent of claim 11, wherein two functional silane linking agents are that dialkyl dialkoxy silicane or dialkyl group two ketoximinosilanes and trifunctional linking agent are alkyltrialkoxysilaneand or alkyl three ketoximinosilanes.
13. sealing agent according to Claim 8 also comprises about 1 to about 10 parts (weight is in per 100 parts of weight acrylamide acid copolymers) aliphatic monohydric alcohols.
14. according to the sealing agent of claim 13, wherein fatty monohydroxy-alcohol is a Virahol.
15. curing sealant according to Claim 8, its tensile strength is at least 1.4MPa, and elongation at break is at least 140%.
16. according to the curing sealant of claim 15, its bonding stripping strength on glass and aluminum substrates surface is at least 2KN/m.
17., passed through ASTM C719 and moved ± 25% test on glass, aluminium and the bottom mortar surface according to the curing sealant of claim 16.
18. curing sealant according to claim 13, its tensile strength is at least 1.4MPa, elongation at break at least 140% is at least 2KN/m at glass and the lip-deep bonding stripping strength of aluminum substrates, passed through ASTM C719 and move ± 25% test on glass, aluminium and bottom sand oar surface.And the elastic recovery rate when 100% elongation is at least 70%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17194693A | 1993-12-22 | 1993-12-22 | |
| US08/171,946 | 1993-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1150810A true CN1150810A (en) | 1997-05-28 |
Family
ID=22625745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94194880A Pending CN1150810A (en) | 1993-12-22 | 1994-12-22 | Moisture-curable modified acrylic polymer sealant composition |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US5705561A (en) |
| EP (1) | EP0736050B1 (en) |
| JP (1) | JP3335359B2 (en) |
| KR (1) | KR100336216B1 (en) |
| CN (1) | CN1150810A (en) |
| AT (1) | ATE171959T1 (en) |
| AU (1) | AU704705B2 (en) |
| BR (1) | BR9408477A (en) |
| CA (1) | CA2179637A1 (en) |
| DE (1) | DE69413849T2 (en) |
| DK (1) | DK0736050T3 (en) |
| ES (1) | ES2127507T3 (en) |
| FI (1) | FI113660B (en) |
| NO (1) | NO315946B1 (en) |
| NZ (1) | NZ277875A (en) |
| RU (1) | RU2144045C1 (en) |
| WO (1) | WO1995017443A1 (en) |
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- 1994-12-22 NZ NZ277875A patent/NZ277875A/en not_active IP Right Cessation
- 1994-12-22 KR KR1019960703406A patent/KR100336216B1/en not_active IP Right Cessation
- 1994-12-22 EP EP95904672A patent/EP0736050B1/en not_active Expired - Lifetime
- 1994-12-22 WO PCT/IB1995/000016 patent/WO1995017443A1/en active IP Right Grant
- 1994-12-22 AT AT95904672T patent/ATE171959T1/en not_active IP Right Cessation
- 1994-12-22 CN CN94194880A patent/CN1150810A/en active Pending
- 1994-12-22 BR BR9408477A patent/BR9408477A/en not_active Application Discontinuation
- 1994-12-22 DK DK95904672T patent/DK0736050T3/en active
- 1994-12-22 DE DE69413849T patent/DE69413849T2/en not_active Expired - Fee Related
- 1994-12-22 CA CA002179637A patent/CA2179637A1/en not_active Abandoned
- 1994-12-22 RU RU96115283A patent/RU2144045C1/en not_active IP Right Cessation
- 1994-12-22 AU AU13262/95A patent/AU704705B2/en not_active Ceased
- 1994-12-22 ES ES95904672T patent/ES2127507T3/en not_active Expired - Lifetime
- 1994-12-22 JP JP51730295A patent/JP3335359B2/en not_active Expired - Fee Related
-
1996
- 1996-06-17 US US08/664,761 patent/US5705561A/en not_active Expired - Fee Related
- 1996-06-20 FI FI962600A patent/FI113660B/en not_active IP Right Cessation
- 1996-06-20 NO NO19962639A patent/NO315946B1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI502031B (en) * | 2012-03-01 | 2015-10-01 | Eternal Materials Co Ltd | Etch-resistant composition and its application |
| CN104448520A (en) * | 2014-11-17 | 2015-03-25 | 浙江万马高分子材料有限公司 | Polyolefin insulating material as well as preparation method and application thereof |
| CN104448520B (en) * | 2014-11-17 | 2017-05-24 | 浙江万马高分子材料有限公司 | Polyolefin insulating material as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2179637A1 (en) | 1995-06-29 |
| JP3335359B2 (en) | 2002-10-15 |
| AU1326295A (en) | 1995-07-10 |
| FI113660B (en) | 2004-05-31 |
| ES2127507T3 (en) | 1999-04-16 |
| NO962639L (en) | 1996-07-30 |
| ATE171959T1 (en) | 1998-10-15 |
| BR9408477A (en) | 1997-03-04 |
| WO1995017443A1 (en) | 1995-06-29 |
| DK0736050T3 (en) | 1999-06-21 |
| DE69413849T2 (en) | 1999-04-29 |
| NZ277875A (en) | 1998-03-25 |
| US5705561A (en) | 1998-01-06 |
| JPH09511264A (en) | 1997-11-11 |
| FI962600A0 (en) | 1996-06-20 |
| NO962639D0 (en) | 1996-06-20 |
| AU704705B2 (en) | 1999-04-29 |
| NO315946B1 (en) | 2003-11-17 |
| EP0736050A1 (en) | 1996-10-09 |
| DE69413849D1 (en) | 1998-11-12 |
| RU2144045C1 (en) | 2000-01-10 |
| EP0736050B1 (en) | 1998-10-07 |
| KR100336216B1 (en) | 2002-10-18 |
| FI962600A (en) | 1996-08-20 |
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